CN101239388A - Non-magnetic cemented carbide powder composed of nickel-tungsten and nickel-chromium binder phase and preparation - Google Patents
Non-magnetic cemented carbide powder composed of nickel-tungsten and nickel-chromium binder phase and preparation Download PDFInfo
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- CN101239388A CN101239388A CNA2008100007908A CN200810000790A CN101239388A CN 101239388 A CN101239388 A CN 101239388A CN A2008100007908 A CNA2008100007908 A CN A2008100007908A CN 200810000790 A CN200810000790 A CN 200810000790A CN 101239388 A CN101239388 A CN 101239388A
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Abstract
The invention relates to nonmagnetic hard alloy powder made of nickel-tungsten, nickel-chromium agglutinate phases, and a producing method thereof. The nonmagnetic hard alloy powder is produced by using nickel-tungsten alloy powder, nickel-tungsten-chromium alloy powder, nickel-chromium alloy powder or nickel-chromium-aluminum alloy as agglutinate phases, using wolfram carbine or wolfram carbine+chromium carbide as a hard phase, then agglomerating or spray drying, and sintering. By using the nonmagnetic hard alloy powder, nonmagnetic hard alloy coats and nonmagnetic hard alloy parts can be produced.
Description
Technical field
Of the present invention is that the technical field that the used for hot spraying non-magnetic cemented carbide powder that constitutes mutually of bonding and coating production relate to is: thermal spraying field of engineering technology, thermal spraying material engineering field, powdered metallurgical material field, non-magnesium hard alloy material field etc. by metallic nickel tungsten, nichrome class.
This dusty material is except that being applicable to that thermal spraying (HVOF, plasma spraying or common flame etc.) technology prepares the non-magnesium hard alloy coating, also prepares the non-magnesium hard alloy parts applicable to the powder metallurgical technique sintering.
Background technology
In the modern industry field, magnetic material has become important basic material.In order to obtain high performance permanent-magnet material, require in the production under high-intensity magnetic field, to suppress, this pattern tool of will hoping for success adopts no magnetic material on certain direction.Over nearly 20 years, produce this no magnetic mould and remove to use outside the nonmagnetic steel (as 1Cr18Ni9Ti, 70Mn, 9Mn9 etc.), people also research and development application WC-Ni be that non-magnesium hard alloy is produced this no magnetic mould.The application of non-magnesium hard alloy mould has improved Magnaglo greatly and has added man-hour, because the mould inner wall that the easily sticking powder of mould is caused produces plucking, so that influences the size granularity and the surface quality of magnetic base.Simultaneously, this non-magnesium hard alloy mould comprehensive mechanical performances such as wearability also at double be higher than stainless steel mould, the service life of having improved mould.But, producing technologic difficult point below preparation non-magnesium hard alloy (WC-Ni) existence at present.
At WC-Ni is that the carbon district in nonmagnetic desired two phase alloys was narrower during non-magnesium hard alloy was produced, and the control that causes carbon content aborning is difficulty very.
The WC-Ni of large volume (more than 10kg) is that the production of non-magnesium hard alloy mould is comparatively difficult.This is because the mould volume is big, and the carbon content inside and outside the mould is uppity evenly.In addition, the non-magnesium hard alloy mould of large volume come unstuck, easy to crack and distortion in the sintering process.
For reducing production WC-Ni is the production difficulty of non-magnesium hard alloy, and people added Cr, Al, Cr in recent years again in WC-Ni
3C
2Deng additive, the adding of these additives mainly is to make the bonding in this kind material become Ni-W-Al mutually, no magnetic phase such as Ni-Cr-Al, but in actual production, factors such as bonding phase Elements Diffusion are difficult to control, make final product not reach the physics and the mechanical performance requirement of expection on performance.
How solving above-mentioned critical technological point, still do not have clearly report at present, is being that close-burning used for hot spraying non-magnetic cemented carbide powder prepares at home and abroad non-avaible report still with nickel tungsten, nichrome alloy type particularly.
Summary of the invention
The purpose of this invention is to provide a kind of nickel tungsten, nickel chromium triangle the bonding non-magnetic cemented carbide powder and the preparation method of formation mutually.
The present invention with the nickel tungsten powder (contain 15～35wt%W), nickel-tungsten-Al alloy powder (contain 15～35wt%W, 3～15wt%Al), nickel-chromium alloy powder (contain 5～45wt%Cr) and the nichrome aluminum alloy powder (contain that arbitrary alloyed powder is the bonding phase among 5～45wt%Cr, 3～15wt%Al), (contain that arbitrary alloyed powder is the hard phase in 10～15wt%Cr3C2) alloy powders with tungsten carbide powder, tungsten carbide-chromium carbide, described bonding accounts for 10～50wt% of this kind non-magnetic cemented carbide powder quality total amount mutually, and hard phase powder accounts for 90～50wt%
Further, described bonding is to be made by atomizing mutually, and powder particle size is 104～2.5 μ m.
Further, described atomizing comprises vacuum atomizing, common atomizing, water atomization.
Further, described hard mutually in various carbide alloy particles of powder degree be 74～1.25 μ m, described tungsten carbide comprises the cast tungsten carbide alloy powder.
Produce a kind of nickel tungsten, the nickel chromium triangle bonding preparation method of the non-magnetic cemented carbide powder of formation mutually, this method may further comprise the steps:
(1) will bond phase powder and hard mutually powder place ball grinder, ball mill mixing 4～72 hours, ratio of grinding media to material is 2: 1～4: 1, the powder that obtains mixing.
(2) powder is carried out spray-drying process, the spray-drying binding agent is polyvinyl alcohol or PEF pyrrole Lip river alkane ketone, and the spray-drying temperature generally is controlled at 150～300 ℃.
(3) this kind non-magnetic cemented carbide powder after the spray-dried granulation carries out vacuum-sintering, and sintering temperature is
900～1400 ℃, sintering time 1～4 hour, product carries out sizing behind the sintering, promptly gets the used for hot spraying non-magnetic cemented carbide powder.
Advantage of the present invention:
This kind powder provided by the invention and coating are lower than on the physics magnetic property does not have magnetic Austriaization body stainless steel (1Cr18Ni9Ti in the market, 70Mn, 9Mn9 etc.), powder bonded with this method preparation distributes comparatively even with hard mutually, the aggregate density height, good fluidity can satisfy the requirement of thermal spraying (HVOF HVOF, plasma thermal sprayed, common flame-spraying) technology.Use this powder can prepare coating densification, non-magnesium hard alloy coating that bond strength is high.
Description of drawings
Figure 1 shows that Ni-W, the preparation of Ni-Cr alloy powder and do not have the process chart that magnetic coating prepares.
Figure 2 shows that the surface topography map (SEM) of the spray-dried non-magnetic cemented carbide powder that makes of Ni-Cr alloyed powder and WC powder.
The specific embodiment
As shown in Figure 1, preparation method of the present invention is as follows:
The preparation of 1 nickel tungsten, nichrome class bonding phase powder
Metal or alloy such as nickel, tungsten, chromium and aluminium by the percentage by weight of required alloy powder, are placed in the smelting furnace (vacuum atomizing will in vacuum melting furnace) to be smelted into alloy solution and then atomize.Vacuum atomizing or common aerosolization inert gas nitrogen or argon, atomization pressure generally is controlled between 1.5～2.5MPa; Water atomization pressure then is controlled at 20～40MPa.Can produce no magnetic nickel tungsten, the nichrome class alloy powder of granularity by above-mentioned melting and atomization process, the non-magnetic alloy powder sieving that is gone out by above-mentioned explained hereafter can be gone out different powder particle size sections according to customer requirement: as 104～2.5 μ m, 74～2.5 μ m or 38～2.5 μ m at 104～2.5 μ m.
2 batch mixings
Above-mentioned nickel tungsten, nichrome class are not had magnetic bonding phase alloy powder and hard phase alloy powder tungsten carbide, tungsten carbide+chromium carbide, carry out the batch mixing ball milling by the weight proportion of customer requirement.Usually these carbide hard phase powder particle sizes are at 38～1.25 μ m, and the Fei Shi granularity of the hard phase carbide alloy powder described in this invention is about 2.5 μ m.Ball-milling medium is an alcohol, ball milling ball ordinary rigid alloying pellet.
Ball, material, medium ratio are 3: 1: 1 in the ball milling.
The ball milling time was generally 12～72 hours.
3 spray-dryings or the granulation of reuniting
Spray-drying: material, glue, water (alcohol) is than the proportioning that is 3: 1: 1, stirs into when temperature reaches 150～280 ℃ in the drying chamber of waiting to spray behind the slip, carries out spray-drying process.
Powder after the spray-drying can carry out screening just on request, and classification is placed and treated down road technology usefulness.
Reunite to granulate: by required bonding phase powder and hard mutually powder weight percentage carry out weighing and put-stirred vessel in, adding binding agent etc., selecting polyurethanes or varnish usually for use is binding agent.Content of binder is 1～2% of total powder weight, curing agent is 0.5～1%, and diluent is 3～5%, above binding agent is inserted in the agitator stir with powder, after reunion is granulated and treated that the powder granulation is solidified, carry out the sieve classification placement on request and treat down road technology usefulness.
4 vacuum-sinterings
With spray-drying or the powder that obtains of reunite granulating be positioned in refractory ceramics jar or the graphite tank body vacuum-sintering.900～1400 ℃ of temperature retention times of sintering temperature 1～4 hour are treated furnace temperature to room temperature, take out powder in the stove, sieve on request again, pack placement respectively by the variable grain particle size range and get final product.
Table 1 is depicted as the proportioning of nickel tungsten, nickel chromium triangle class non-magnesium hard alloy, and the proportioning content of the non-magnesium hard alloy among the present invention is according to the carrying out shown in the table 1.
Table 1 nickel tungsten, nickel chromium triangle class non-magnesium hard alloy proportioning table
| Bonding phase classification | Bonding phase content/the wt% of alloy | Alloy hard phase content/wt% | |
| WC | Cr 3C 2 | ||
| The NiW class (contains 15～20wt%W) | 12～17 | 88～83 | - |
| 78～68 | 10～15 | ||
| 20～25 | 80～75 | - | |
| 70～60 | 10～15- | ||
| 25～50 | 75～50 | - | |
| 65～35 | 10～15 | ||
| The NiWAl class (contains 15～20wt%W, 3～15wt%Al) | 12～17 | 88～83 | - |
| 78～68 | 10～15 | ||
| 20～25 | 80～75 | - | |
| 70～60 | 10～15- | ||
| 25～50 | 75～50 | - | |
| 65～35 | 10～15 | ||
| The NiCr class (contains 5～45%Cr) | 12～17 | 88～83 | - |
| 78～68 | 10～15 | ||
| 20～25 | 80～75 | - | |
| 70～60 | 10～15- | ||
| 25～50 | 75～50 | - | |
| 65～35 | 10～15 | ||
| The NiCrAl class (contains 5～45%Cr, 3～15wt%Al) | 12～17 | 88～83 | - |
| 78～68 | 10～15 | ||
| 20～25 | 80～75 | - | |
| 70～60 | 10～15- | ||
| 25～50 | 75～50 | - | |
| 65～35 | 10～15 |
Embodiment 1
1 atomizing
Nickel, tungsten metal are placed in the smelting furnace by mass ratio at 4: 1, carry out common aerosolization after being smelted into alloy solution.Atomizing is a nitrogen with inert gas, and gas pressure generally is controlled between 1.5～2.5MPa, afterwards the nickel tungsten of producing is not had magnetic bonding phase alloy powder and sieves.
2 batch mixings
Select for use granularity less than the nickel tungsten powder of 30 μ m (W content is 15～20wt%) to be bonding phase powder, and granularity is a hard phase powder less than the tungsten carbide of 2.7 μ m, and the quality of two kinds of powder accounts for 12%, 88% respectively, after carry out the batch mixing ball milling.Ball-milling medium is an absolute ethyl alcohol, and ball, material, medium ratio are 3: 1: 1 in the ball milling, and the ball milling time is 48 hours.
3 spray-dryings
With the mixed powder of ball milling according to material, glue, water (alcohol) than the proportioning that is 3: 1: 1, stirred 20～30 minutes, glue is selected polyvinyl alcohol for use, adopts the centrifugal spray drying method to granulate afterwards.Wherein the spray-drying temperature is 150～280 ℃.Sieve as required afterwards.
4 vacuum-sinterings
Powder after the spray-drying is positioned in refractory ceramics jar or the graphite tank body, carries out vacuum-sintering.Sintering temperature is 1000～1300 ℃, and vacuum is 5～10Pa, temperature retention time 2～34 hours.The back screening obtains the powder of 15～45 μ m and 45～75 μ m.
Embodiment 2
1 atomizing
Nickel, tungsten metal are placed in the smelting furnace by mass ratio at 4: 1, carry out common aerosolization after being smelted into alloy solution.Atomizing is a nitrogen with inert gas, and gas pressure generally is controlled between 1.5～2.5MPa, afterwards the nickel tungsten of producing is not had magnetic bonding phase alloy powder and sieves.
2 batch mixings
Select for use granularity less than the nickel tungsten powder of 30 μ m (W content is 15～20wt%) to be bonding phase powder, and granularity is a hard phase powder less than the tungsten carbide of 2.7 μ m, and the quality of two kinds of powder accounts for 20%, 80% respectively, after carry out the batch mixing ball milling.Ball-milling medium is an absolute ethyl alcohol, and ball, material, medium ratio are 3: 1: 1 in the ball milling, and the ball milling time is 48 hours.
3 spray-dryings
With the mixed powder of ball milling according to material, glue, water (alcohol) than the proportioning that is 3: 1: 1, stirred 20～30 minutes, glue is selected polyvinyl alcohol for use, adopts the centrifugal spray drying method to granulate afterwards.Wherein the spray-drying temperature is 150～280 ℃.Sieve as required afterwards.
4 vacuum-sinterings
Powder after the spray-drying is positioned in refractory ceramics jar or the graphite tank body, carries out vacuum-sintering.Sintering temperature is 1000～1300 ℃, and vacuum is 5～10Pa, temperature retention time 2～34 hours.The back screening obtains the powder of 1 5～45 μ m and 45～75 μ m.
Embodiment 3
1 atomizing
Nickel, tungsten metal are placed in the smelting furnace by mass ratio at 4: 1, carry out common aerosolization after being smelted into alloy solution.Atomizing is a nitrogen with inert gas, and gas pressure generally is controlled between 1.5～2.5MPa, afterwards the nickel tungsten of producing is not had magnetic bonding phase alloy powder and sieves.
2 batch mixings
Select for use granularity less than the nickel tungsten powder of 30 μ m (W content is 15～20wt%) to be bonding phase powder, and granularity is a hard phase powder less than the tungsten carbide of 2.7 μ m, and the quality of two kinds of powder accounts for 50%, 50% respectively, after carry out the batch mixing ball milling.Ball-milling medium is an absolute ethyl alcohol, and ball, material, medium ratio are 3: 1: 1 in the ball milling, and the ball milling time is 48 hours.
3 spray-dryings
With the mixed powder of ball milling according to material, glue, water (alcohol) than the proportioning that is 3: 1: 1, stirred 20～30 minutes, glue is selected polyvinyl alcohol for use, adopts the centrifugal spray drying method to granulate afterwards.Wherein the spray-drying temperature is 150～280 ℃.Sieve as required afterwards.
4 vacuum-sinterings
Powder after the spray-drying is positioned in refractory ceramics jar or the graphite tank body, carries out vacuum-sintering.Sintering temperature is 1000～1300 ℃, and vacuum is 5～10Pa, temperature retention time 2～34 hours.The back screening obtains the powder of 15～45 μ m and 45～75 μ m.
Claims (5)
1. the non-magnetic cemented carbide powder that constitutes mutually of a nickel tungsten, nickel chromium triangle bonding, it is characterized in that with the nickel tungsten powder (contain 15～35wt%W), nickel-tungsten-Al alloy powder (contain 15～35wt%W, 3～15wt%Al), nickel-chromium alloy powder (contain 5～45wt%Cr) and the nichrome aluminum alloy powder (contain that arbitrary alloyed powder is the bonding phase among 5～45wt%Cr, 3～15wt%Al), (contain 10～15wt%Cr with tungsten carbide powder, tungsten carbide-chromium carbide
3C
2) arbitrary alloyed powder is the hard phase in the alloy powder, described bonding accounts for 10～50wt% of this kind non-magnetic cemented carbide powder quality total amount mutually, and hard phase powder accounts for 90～50wt%.
2. the non-magnetic cemented carbide powder that a kind of nickel tungsten according to claim 1, nickel chromium triangle bonding constitute mutually is characterized in that described bonding is to be made by atomizing mutually, and powder particle size is 104～2.5 μ m.
3, the non-magnetic cemented carbide powder that constitutes mutually of a kind of nickel tungsten according to claim 2, nickel chromium triangle bonding is characterized in that described atomizing comprises vacuum atomizing, common atomizing, water atomization.
4. the non-magnetic cemented carbide powder that a kind of nickel tungsten according to claim 1, nickel chromium triangle bonding constitute mutually, it is characterized in that various carbide alloy particles of powder degree are 74～1.25 μ m during described hard mutually, described tungsten carbide comprises the cast tungsten carbide alloy powder.
5. produce the preparation method of this kind used for hot spraying non-magnetic cemented carbide powder as claimed in claim 1, it is characterized in that this method may further comprise the steps:
(1) will bond phase powder and hard mutually powder place ball grinder, ball mill mixing 4～72 hours, ratio of grinding media to material is 2: 1～4: 1, the powder that obtains mixing.
(2) powder is carried out spray-drying process, the spray-drying binding agent is polyvinyl alcohol or PEF pyrrole Lip river alkane ketone, and the spray-drying temperature generally is controlled at 150～300 ℃.
(3) this kind non-magnetic cemented carbide powder after the spray-dried granulation carries out vacuum-sintering, and sintering temperature is 900～1400 ℃, sintering time 1～4 hour, and product carries out sizing behind the sintering, promptly gets the used for hot spraying non-magnetic cemented carbide powder.
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